Dehydrofluorination process



2 sx-IEETs-SHEET 1 Filed Dec. 18, 1947 Oct. 23, 1951 G. N. CADE 2,572,595

'DEHYDROFLUORINATION PRocEss Filed nec. 18, 1947 2 SHEETS-SHEET 2 JNVENTOR.

G.N.CADE

ATTORNEYS Patented Oct. 23, 1951 DEHYDROFLUORINATION PROCESS George N. Cade, Bartlesville, Okla., assignor to Phillips Petroleum Company, a, corporation of Delaware Application December 18, 1947, Serial No. 792,592

1o claims. l

This invention relates to the treatment of hydrocarbons. In one of its more specific aspects, it relates to the treatment of hydrocarbon materials containing organically combined lluorine for the removal and recovery of said halogen. In a still more specic aspect, it relates to a process for the removal and recovery of organically combined fluorine from products of alkylation or isomerization wherein a fluoride has been used as a catalyst.

The presence of small amounts of organically combined uorine in hydrocarbon products of alkylation, of isomerization, and of other reactions promoted by halide catalysts and the undesirability of these iiuorine compounds in the hydrocarbon products are known in the art. In certain processes, such as HF alkylation, the removal of organic iiuorine from the products is particularly important. In the past, the iiuorine has been removed by one of several methods: (l) thermal decomposition, (2) treatment with granular porous oxides, such as bauxite, and (3) treatment with metals or mixtures of metals. The rst type is disadvantageous in that it may be accompanied by corrosion of equipment and, in some cases, undesired reactions of the hydrocarbons. The second, although efective, is disadvantageous in that recovery of the removed uorine in useful form is diiicult and in that some naturally occurring oxides contain siliceous impurities that are converted to undesired silicon tetrauoride. The third method comprises contacting the hydrocarbon products with metal catalysts that effect the splitting of hydrogen fluoride from the organic halogen compounds; the hydrogen fluoride split 01T may be subsequently recovered as such and reused as the catalyst or component thereof. This latter method has the further advantage that HF-producing reaction is not accompanied by silicon tetraluoride formation.

One limitation in the use of metals or mixtures of metals as catalysts for hydrogen iiuoride recovery is that the metal catalysts have heretofore been used in the form of rather coarse metals, and, of course, in such condition they have a small surface area per unit Weight. Furthermore, these catalysts have heretofore been used only in static, iixed-bed operation, in which the hydrocarbon treated contacts only a relatively small part of the catalyst. As a result, contact of the hydrocarbons with the catalyst is somewhat limited, and comparatively low space velocities are necessary for obtaining the desired extent of dehydroiiuorination.

i a method for the effective removal of organically combined fluorine from hydrocarbon materials containing such products and for the recovery of such removed fluorine.

Another object of my invention is to provide a process for increasing the effectiveness of the contacting of the organic fluorine-containing hydrocarbon material with the reagent to expedite removal of the iluorine. i

Still another object of my invention is to provide a continuous process for such luorine removal and recovery.

Still other obJects and advantages will be apparent upon reading the following disclosure, which taken with the attached drawing, respectively described and illustrates preferred form o my invention.

Figure 1 or" the drawing represents diagrammatically one form of apparatus in which one embodiment of my invention may be carried out.

Figure 2 represents diagrammatically another form of apparatus in which a second embodiment of my invention may be carried out.

The present invention provides a dehydrofluorination process in which improved contacting of the hydrocarbon With the catalyst is obtainable and in which increased space velocities may be used. In accordance with one embodiment of my invention, hydrocarbons are contacted in the vapor phase, with a fluidized metallic dehydroluorination catalyst having a relatively high surface area per unit of weight, and with a fluidized hydrogen fluoride adsorbent at temperaures and pressures suitable for dehydrofluorination. The adsorbent is subsequently heated at an increased temperature, preferably in the presence of a carrier gas to desorb the hydrogen iiuoride, which may be recovered.

Another embodiment of my invention provides for a method of dehydroiiuorination with improved contacting in the presence of a metal catalyst also having a relatively high surface area per unit of weight. In this embodiment, the finely divided metal catalyst is added to the liquid hydrocarbon to be treated in the form of a slurry and this mixture then subjected to dehydrofluorination conditions. The metal catalyst is then settled, Withdrawn from the settler and recycled. The liberated hydrogen fluoride may `then be removed by distillation for cyclic 3 use in a prior step of the process or for such other disposal as desired.

By organically combined lluorine, I include the type of compounds ordinarily called organic fluorides, such as, for example, ethyl fluoride, propyl luoride, either normal or iso, butyl fluoride, either normal, secondary, or iso. Such compounds are formed, to a small extent, in such catalytic processes as hydrogen fluoride alkylation, isomerization, or other processes in which a iluoride catalyst is contacted with hy drocarbon compounds.

By the term dehydroiluorination is meant the splitting off of hydrogen uoride from a fluo# rine containing compound, such as butyl fluoride, propyl fluoride, etc. It is believed that when HF splits off from butyl fluoride V(-(tI-Itl),

a butene (04H8) is produced. Although one embodiment is herein described in connection with a hydrocarbon isomerization catalyzed by hydrofluoric acid and boronfluoride, it may alsoy be practiced in conjunction with other fluoridecatalyzed conversions, suchas hydrouoric acid alkylation and the like.

In some instances, particularly when relatively high-boiling materials are present in the products of a lluoride-catalyzed conversion, it may be desirable to treat only the lower-boiling fractions of the hydrocarbon product by the process of this invention, sinc-e in some case-s, v'

cost of the organic uorine is concentrated in these fractions.

Referring to the drawing and especially to Figure l, which is a schematic flow diagram of one embodiment of my invention, normal pentane and a catalyst, comprising about 97 per cent hydroiluoric acid and 3 per cent by weight of boron fluoride, enter a reactor l!! through inlets i2 and I3, res-pectively. In reactor I4, which is maintained at about 100 F. and under sufcient pressure to maintain substantially all the contents in the liquid phase, the normall pentane is intimately contacted withy the catalyst and converted to isopentane, butanes, and hexanes. The reactor euentis passed through a conduit l5 intoa settler lil, in which th-e mixture separates` into a heavy acid phase and a lighter hydrocarbon phase. Most'of the acid phase is recycled through a conduit i8 to the reactor I4; the remainder is withdrawn through an outlet Il and passed to regeneration means, not shown. The hydrocarbon phase from the settler I6 is passed through a conduit I9 to an azeotropic distillation column 2E). From this distillation column, an overhead fraction comprising a minimum-boiling azeotropic mixture of isobutane and hydroluoric acid is withdrawn through a conduit 2i, condensed in a condenser #i9 and passed to an accumulator 22, in which it separates into an acid phase and a hydrocarbon phase. The acid phase is recycled through a conduit 24 to the settler I6 and the hydrocarbon phase is returned to the column as reflux through a conduit 23. A substantially acidfree kettle product is passed through. a conduit 25 to a heater 25 in which the bottoms product is vaporized. The vaporized hydrocarbon mixture then is passed through a conduit 25A to a treater 28.

The treater 28 comprises two sections, an upper or cylindrical section and a lower or conical section. The lower or conical section contains metal (e. g. zinc) catalyst 38 is substantially dust or nely divided form, and the upper cylindrical portion of the treater contains nely Lil) divided activated carbon 39. Since the linear velocities of the hydrocarbon material in the conical section of the treater is greater than in the cylindrical section and since the density of the activated carbon is considerably lower than that of the zinc dust, the activated carbon concentrates in the upper section of the treater and, accordingly, the zinc dust concentrates in the lower section. The velocities of the'J hydrocarbon gases passing through the treater 28 and the particle size of the metal dust and of the activated carbon are so interrelated that the described concentration occurs and that these two solid? materials are maintained in a state of fluidization or hindered settling in the hydrocarbon material passing through the treater. It is intended that little or no solid material is carried out of the treater 28 by the hydrocarbon material. If, however, any solid material is carried out, it may be separated by conventional meansA and returned. to the treater through connecting pipes etc., not shown. When charging the treater 28 or when. adding fresh catalyst and adsorbent during operation, these materials may be added through a valved inlet line 49. A carrier gas also passes through the line el) in suicient velocity to carry the catalyst and adsorbent throughv the pipe Il@ through a pipe 25A into theA conical section of the treater 28. As additional solid materials are addedfthrough line lo and passed into the treater 28, the depthA of the solid. beds increases until the desired amount of the catalyst and adsorbent have been added.

During operation, used adsorbent may be withdrawn from the treater 28 through a line 4| and passed into a regenerator 45. In this regenerator, the adsorbent may be heated to strip off the adsorbed material, which, in this case, will be hydrogen fluoride, and this material may pass through. line 50 into a condenser 33.. Adsorbent freed of its adsorbedv material in regenerator l5 passes through a line 46 into the, line 49 for recycling into the treater vessel 2.8.

In like manner, used finely divided metal may be withdrawn from. the treater 28 through a pipe 42 and passedy into. a regenerator means 48 in which the. metal may be revivied by any means desired.. Thev revivied` metal isl then passed through a conduit 4l into the conduit 8 to be readded to the main bulk of metal catalyst in the treater 28. YAny. hydrocarbon material withdrawn through the outlets 4| and l2 may be recovered in conjunction with the regenerator means 45 and L38, if desired.

The above-described concentration of the nely divided zinc in the lower portionv of the treater 28 and of the activated carbon in the upper section of the treater 28. constitute a particularly advantageous feature of the present invention.v The finely divided zinc catalyzes the dehydrofluorination reaction in the lower section of the treater 28, and the hydrogen fluoride so liberated isv adsorbed by the activated carbon in the upper section of the treater 28. The` dehydroluorination and the hydrogen fluoride adsorption are thus accomplished in a single treater and Without the necessity for previously arranged alternate xed bedsY of catalyst and adsorbent. An additional advantage. of this treater 28 is that its capacity is much greater for a given size of vessel than thatV of the static, fixed-bed type of apparatus. The deluorinated hydrocarbon material is withdrawn` from the treater 28 through a. conduit 29. A portion of the material in conduit 29 may be recycled to theL treater 28 through a conduit 50A, if desired. Substantially fluorinefree hydrocarbon material is withdrawn from the system through an outlet line and is passed to a fractionation means, not shown, for recovery of desired hydrocarbons or hydrocarbon fractions.

In one modification, when the activated carbon 39 has become saturated with the hydrogen iluoride, the valves 2l and 3l in conduits 25A and 30, respectively, are closed and the vaporized hydrocarbon material may be passed to a stand-by treater, not shown, but similar to the treater 28. Valves 31 and 32, previously closed, in inlet 36 and conduit 29, respectively, are then opened. A hot carrier gas introduced through the inlet 3B passes through the finely divided zinc 38 and nally contacts the activated carbon 39 to desorb and carry away the hydrogen fluoride. The carrier gas containing the hydrogen fluoride is passed through the conduit 29 to the condenser 33 for condensation of the hydrogen fluoride. The carrier gas itself may be withdrawn from the system through an outlet 34, and the condensed hydrogen iiuoride is passed through a conduit to reactor I4.

Light hydrocarbons and/or other inert gases, such as nitrogen or hydrogen, may be used as the carrier gas. A preferred carrier gas is a part of the normal pentane feed to the reactor I4. When normal pentane is so used, the partial condenser 33 may be modified or eliminated and the pentane-hydrogen iluoride mixture eiiluent from treater 28 may be totally condensed and passed directly to the reactor I4.

When such a stand-by treater is used in conjunction with the treater 28, the regenerators and 48 need not be used. However, I prefer to K use regenerators such as those illustrated diagrammatically as regenerators 45 and 48 and save the cost of construction of a double treater Vessel. It will be understood that treater 28 and regenerators 45 and 48 are illustrated diagrammatically and that means for removal and return of the carbon and the zinc are not described in detail, since such means are known in the art.

In this preferred embodiment, the dehydrofluorination and hydrogen fluoride adsorption are conducted in a single treater vessel. A suitable temperature range for the dehydrofluorination and for the activated carbon is from about 150 to 350 F. The pressure is not critical, although in general, extremely high pressures disfavor the hydroiluorination reaction and favor adsorption. Pressures from atmospheric up to 100 pounds per square inch, or even more, may be used. The space velocities of the hydrocarbon vapors passing through treater 28 may be of the order of 1000' to 3000 gaseous volumes of hydrocarbon per volume of catalyst plus adsorbent per hour. The optimum space velocities for any particular application, however, will depend upon such factors as the particular catalyst used, the particular adsorbent used, the particle size of these materials, and the design of the treater and should probably best be determined by trial. Fluid-bed or hindered settling conditions in treater 28 are preferred. The treater may, however, be operated at such conditions that the adsorbent is carried through the treater in suspension in the hydrocarbon, separated from the hydrocarbon stream, and recycled to the treater.

The desorption of the hydrogen fluoride from the enriched adsorbent may be carried out in either the regenerator vesse145 or in the main treater vessel 28 at temperatures ranging fromabout 350 to 500 F. Desorption in either' case. of course, is promoted by the use of carrier gas. Atmospheric pressure is suitable for desorption although higher pressures may be used, if desired. Desorption is, of course, favored by relatively low pressure. Fluidizing space velocities may be used during the desorption. Lower pressure, however, may also be used.

As dehydrofluorination catalysts, I prefer metals of about 40 to 250 mesh size. Examples of such metals that are suitable and commercially available are zinc dust, magnesium powder, and copper and aluminum bronze powders, of the type used in certain paints. It is advantageous, in some cases, to employ a mixture of two or more of these materials. Commercial metals frequently contain other metals in smaller amounts as impurities, and such a metal with metallic impurities is desirable as a catalyst for this process; for example, commercial zinc dust may contain appreciable quantities of lead, copper, or cadmium. Such a zinc catalyst may be prepared from lowgrade spelter. Another useful type of finely divided catalyst consists of metals in the sponge form.

Preferred adsorbent or absorbent materials for use in the upper section of the treater 28 are linely .divided alkali-metal fluorides, cupric sulfate, cuprous chloride, and activated carbon. The lastmentioned material is preferred in the process of the present invention.

Example I Normal pentane is contacted with a catalyst consisting of about 97 Weight per cent hydrouoric acid and 3 weight per cent boron fluoride for about 6 minutes at 118 F. The hydrocarbon product of this reaction, after being freed of the catalyst, has approximately the following composition:

Propane mol per cent 3.2 Isobutane do 42.0 Normal butane do 11.5 Isopentane do 19.6 Normal pentane do 5.5 Isohexanes do 12.7 Heavier do 5.5 Organic F weight, per cent" 0.0702

This hydrocarbon product is substantially completely vaporized and is contacted at 250 F. `and atmospheric pressure with 20G-mesh Zinc dust and GO-mesh activated carbon under fluidizing conditions in a treater similar to treater 28 of Figure 1. The hydrocarbon mixture to be treated is substantially acid-free. After the dehydroiluorination has continued for several hours, small amounts of hydroiiuoric acid are detected in the treated hydrocarbon material. Dehydroiluorination is then discontinued and the carbon-Zinc dust mixture is treated with normal butane at 500 F. until the eiiluent butane contains substantially no acid. Approximately per cent of the organic iuorine removed from the treated hydrocarbon mixture is recovered from the butane as hydrouoric acid.

Additional modications of the embodiment of Figure 1 of my invention will be apparent to those skilled in the art; for example, treater 28 may have the form of an inverted cone, or may comprise two connected cylindrical segments, the upper of which has a substantially greater diameter than the lower. Furthermore, part of the heat added to the hydrocarbon material in con-- duit 25 may be supplied by indirect heat exchangewith adsorbent and dehydrouorination catalystimmediately after the desorptionstep or with `the eiiluent carrier gas from the .desorption step.

FigureZ represents a second embodiment ofmy invention and in this embodiment, .the .finely divided metal dust is added to a hydrocarbon liquid to form a slurry and this .slurryis then added to the main quantity of hydrocarbon liquid containing organically combined uorine. Referring to Figure `2, in a contacter 52, the acid-free hydrocarbon material to be freed from organically combined fluorine is .intimately mixed witha slurry of Sfinely vdivided Zinc in liquid hydrocarbons. After 'a suitable reaction period under .dehydrouorination conditions, previously described, the mixture from the mixer 52 vis passed vthrough a conduit .53 to a settler 55 inwhi'ch the Anely ldivided .zinc lis allowed to settle. The zinc and a small'amount .of hydrocarbon is withdrawn from the settler '54 asa slurry and is passed :through lines 66, 65 and 5I into the original c0ntactor52. A portion :of this slurry, however, may be with drawn through an outlet 61 for recovery .of the hydrocarbons and discarding of the zinc or for revivcation of the zinc in means not shown. The settler 54 is maintained at such temperature and pressure that `substantially all the hydroiiu oric .acid liberated in the contacter 52 .is flashed off as a minimum-boiling azeotropic mixture with isobutane and/or propane. The flashed acidhydrocarbon mixture is passed Vthrough a conduit 55 to such disposal as desired. In case the liquid-solid contacting embodiment of Figure 2 is used to replace the vapor-solid contacting embodiment of Figure 1, the flashed azeotrope from conduit 55 is then passed through condenser A9 of Figure l and the condensate accumulates in the separator 22. The liquid hydrocarbonmaterial to be treated in conduit in this case, may originate as the bottoms product in the azeotropic distillation column of Figure l, and pipe 25 of Figure 'l would then be connected with pipe 5I of Figure 2.

From the settler 511, Va Substantially fluorinefree hydrocarbon mixture is Vpassed through a conduit 56 into a fractionator 57. The following fractions'may be obtained from this fractionator 51, if desired: (1) a light hydrocarbon fraction, comprising chieily propane, Withdrawn through outlet 58; (2) an isobutane fraction, withdrawn through outlet 5t for such disposal as desired; (3) a normal butane fraction, withdrawn through outlet vEi; (4) a gasoline boiling range fraction, Withdrawn as the main product of the process through outlet 6i; and (5) a heavier fraction, withdrawn through outlet 62.

At least a portion of the heavier fraction is passed through conduit 63 to mixing tank 64, which is provided with a hopper 'B5 and a suitable mixing means, such as the mechanical stirrer 68. Finely divided Zinc, about 200-mesh, is added through the hopper 69 to the heavier hydrocarbon fraction with which the zinc is mixed to form a slurry. Other liquid hydrocarbon may be ladded to the mixing tank t@ `in case insulcient heavy hydrocarbon is available from fractionator 5l for making a slurry of the proper consistency. The slurry is passed through a conduit 65 to conduit 5l to the contacter .52 for the dehydrouorination treatment previously described. .The slurry may be preheated to a dehydrouorination temperature by means not shown. The slurry formation is, however, preferably conducted at about atmospheric Vtemper-v ature and pressureand the slurry heated just prior' to contacting the organic Viiuorine-containing .liquid in conduit. 5l.

.For'use with the vItype of contacter illustrated in the embodiment of Figure 2, .a preferred dehydroiiuorinaton catalyst comprises metals in the form of powders or dust of about 60- to 250 mesh size. .Commercial zinc dust isa suitable and rreadily `available catalyst. Powdered aluminum, such as the so-called aluminum bronze, as used in paints,is also suitable. 'The mixture of two or more powdered metals as a polymetallic dust, such as zinc dust containing appreciable portions of copper or cadmium as impurities is suitable and, .in some cases, may be preferred.

A particularly eiective catalyst may be prepared as follows: To an acidic aqueous solution of metallic salts, such as cadmium, lead, and copper chlorides, is added an excess of a `more electropositive metal in finely divided form, e. lg. commercial `zinc dust, to precipitate substantially all of the cadmium, copper, and lead in the socalled sponge form. The pH of the solution is preferably maintained at about A2 to 4 during the precipitation. The precipitate is separated from the solution, washed, and dried in a nonoxidizing atmosphere. The dried precipitate is then ground to about 60 to 200 mesh size, also ina nonoxidizing atmosphere.

Other specic arrangements within the scope of the invention maybe provided by those skilled in the art; for example, any other or all of the fractions obtained in the fractionator 5'! may be treated individually with the metal slurry in place of treating the feed stream to lthe fractionator. In other cases, when equipment capacity is limited, it may bepreferable to dehydroilourinate only the normally liquid fraction of the hydrocarbon product, and in such as case, it

may be desirable to add a `small amount of light i" hydrocarbon to the metal-treated hydrocarbon to vaid in volatilizing the hydrouoric acid from the settler 54. Furthermore, contacter 52 Amay be so 'constructed "and operated `that the hydrogen fluoride is flashed oi Within the contactor as soon as liberated.

Example II The acid-free hydrocarbon eiliuent from an HF alkylation system in which isobutane is alkylated with butenes contains about 0.03 weight per cent organic uorine. To this eilluent is added a slurry made by mixing commercial zinc .dust with heavy alkylate (I. B. .P. 375 F.) obtained by fractionating the alkylation product. The .zinc dust contains per .cent metallic zinc, 0.2 .per cent lead, 0.15 per cent cadmium, and a trace .of copper; 98 per cent is suciently line to pass through a 22S-mesh screen. The mixture of alkylation effluent and slurry (zinc content of total mixture, 40 Weight per cent) is thoroughly agitated for 20 minutes at 250 F. and 400 p. s. i. by means of a motor-driven stirrer. The liberated hydrofluoric acid is iiashed from the mixture, and the zinc dust is removed by settling and decantation. The rrecovered hydrocarbon .mixture has an organic iiuorine content of about 0.01 weight per cent.

Example ,III

Example II is repeated, a mixture of equal parts Vby weight of 3D-mesh aluminum and copper powders being substituted for .zinc dust, and the contact time being increase to 30 minutes. The recovered hydrocarbon eiiluent has an organic uorine content of about-0.007 weight per cent.

Example IV Example II is repeated as a continuous operation, with the additional step of recycling about 30 volume per cent of the zinc-treated alkylation eiiiuent to the dehydrofluorination step, the recycled material containing, in suspension, substantially allthe settled zinc dust. After establishment of constant operating conditions, the hydrocarbon mixture withdrawn from the system contains substantially less organic fluorine than those previously treated.

I claim:

1. A method for catalytically treating a saturated hydrocarbon material containing saturated iluorine containing organic compounds as impurity for the removal of said impurity comprising maintaining a body of at least one finely divided metal catalyst selected from the group of metals consisting of zinc, magnesium, cadmium, copper, lead and aluminum, in a fluidized condition in a treating zone at a temperature between the limits of 150 F. and 350 F., passing said saturated hydrocarbon material containing said impurity in a vaporous condition at a temperature between the limits of 150 F. and 350 F. into said body of fluidized metal catalyst in said zone to decompose the organic uorine compounds and liberate hydrogen fluoride, immediately separating the liberated hydrogen fluoride from the hydrocarbon vapors by passing the eiiluent vapors from the fluidized metal catalyst through a uidized body of activated carbon in said zone above and in contact with said metal catalyst, and removing treated hydrocarbon material from the body of activated carbon in said zone as the product of the process.

2. The method of claim 1 wherein the space velocity of the vaporous hydrocarbon material containing said impurity passed into the body of fluidized metal in said zone is maintained between the limits of 1000 and 3000 gaseous volumes of hydrocarbon per volume of iinely divided metal and adsorbent per hour.

3. A method for catalytically treating a saturated hydrocarbon material containing saturated fluorine containing organic compounds as impurity for the removal of said impurity comprising maintaining a body of finely divided zinc catalyst in a uidized condition in a treating zone at a temperature between the limits of 150 F. and 350 F., passing said saturated hydrocarbon material containing said impurity in a vaporous condition at a temperature between the limits of 150 and 350 F. into said body of fluidized zinc catalyst in said Zone to decompose the organic uorine compounds and liberate hydrogen fluoride, immediately separating the liberated hydrogen fluoride from the hydrocarbon vapors by passing the effluent vapors from the fluidized zinc catalyst through a iiuidized body of activated carbon in said zone above and in contact with lsaid zinc catalyst, and removing treated hydrocarbon material from the body of activated carbon in said zone as the product of the process.

4. The method of claim 3 wherein the finely divided zinc is 40 mesh and ner in size and the space velocity of the vaporous hydrocarbon material containing said impurity passed into the body of uidized metal in said Zone is maintained between the limits of 1000 and 3000 gaseous volumes of hydrocarbon per volume of finely divided zinc and adsorbent per hour.

5. The method of claim 4 wherein a continuous stream of fluidized activated carbon is removed from said body of fluidized activated car- 10 l bon in said zone and heated to a temperature within the limits of 350 F. and 500 F. to desorb hydrogen fluoride therefrom and to reactivate the carbon, the desorbed reactivated carbon is recycled to the body of activated carbon in said zone, a stream of used finely divided zinc is continuously removed, and such a quantity of fresh finely divided zinc as to replace that removed is continuously added to the fluidized body of finely divided zinc.

6. The method of claim 1 wherein the finely divided metal is in the sponge form.

7. A method for catalytically treating a saturated hydrocarbon material containing saturated uorine containing organic compounds as impurity for the removal of said impurity comprising maintaining a body of nely divided magnesium catalyst in a uidized condition in a treating zone at a temperature between the limits of F. and 350 F., passing said saturated hydrocarbon material containing said impurity in a vaporous condition at a temperature between the limits of 150 and 350 F. into said body of uidized magnesium catalyst in said Zone to decompose the organic uorine compounds and liberate hydrogen fluoride, immediate separating the liberated hydrogen uoride from the hydrocarbon vapors by passing the effluent vapors from the fluidized magnesium catalyst through a iiuidized body of activated carbon in said zone above and in contact with said magnesium catalyst, and removing treated hydrocarbon material from the body of activated carbon in said zone as the product of the process.

8. A method for catalytically treating a saturated hydrocarbon material containing saturated uorine containing organic compounds as impurity for the removal of said impurity comprising maintaining a body of finely divided copper catalyst in a fluidi'zed condition in a treating zone at a temperature between the limits of 150 F. and 350 F., passing said saturated hydrocarbon material containing said impurity in a vaporous condition at a temperature between the limits of 150 and 350 F. into said body of fluidized copper catalyst in said zone to decompose the organic fluorine compounds and liberate hvdrogen uoride, immediately separating the liberated hydrogen fluoride from the hydrocarbon vapors by passing the eiuent vapors from the fluidized copper catalyst through a fiuidized body of activated carbon in said zone above and in contact with said copper catalyst, and removing treated hydrocarbon material from the body of activated carbon in said zone as the product of the process.

9. A method for catalytically treating a saturated hydrocarbon material containing saturated fluorine containing organic compounds as impurity for the removal of said impurity comprising maintaining a body of nely divided lead catalyst in a fluidized condition in a treating zone at a temperature between the limits of 150 F. and 350 F., passing said saturated hydrocarbon material containing said impurity in a vaporous condition at a temperature between the limits of 150 and 350 F. into said body of uidized lead catalyst in said zone to decompose the organic uorine compounds and liberate hydrogen fluoride, immediately separating the liberated hydrogen fluoride from the hydrocarbon vapors by passing the eiuent vapors from the uidized lead catalyst through a uidized body of activated carbon in said zone above and in contact with said lead catalyst, and removing 1l treated hydrocarbon material from the" body of activated carbon in saidV zone as the product of the process;

10. A method for' catalytically treated a `sato-- rated hydrocarbonv material containing saturated uori'ne containing organic compounds as im'- purty for the removalY of said impurity comprising maintaining a body of nely divided aluminum-catalyst in a fluidizedV condition in a treating zone at a temperature between the" limits of 150'F. and 350 F., passing said'saturatedhydrocarbon material containingY said impurity in a vaporous condition'ata temperaturefbetween 'the limitsfof 150 and 350 F. into said body of udized aluminum catalystA in said zoneto decompose the organic'uorine-compounds and'liberate hydrogen fluoride, immediately separating the liberated hydrogen fluoride from the hydrocarbon vapors yby' passing: the eiuent vapors from the uidize'd aluminum catalystthrough a fluidizecl body of activated' carbon in saidzone-above and in contact with said aluminum catalyst, and

removing treated hydrocarbon materialY from the body of activated carbon in saidV zone as* the product of the process.

GEORGE" N; CADE.'

112 REFERENCES CITED The following references are of record: in the le'of this patent.`

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1,801,213- Teplilz- Apr.. 14:, 1931 1,869,781 Shiler. Aug. 2, 1932 1,884,002 Leyes Oct. 25, 1932 2,322,800 Frey June 29, 19.43 2,333,648 Grosse No\l. 9,1943 2,333,649 Grosse Nov; 9,1943 2,341,567 Moriarty ,1eb.Y 15, 1944 2,347,945 Frey May 2r', 1944 2,379,697 Evans .V July 3, 1945 2,379,708 Hearne. July 3,V 1945 2,387,723 Dreyfus Oct.Y 30,A 1945 2,409,690 Nicholson Oct. 22, 1946 2,481,207 Eberle Sept. 6, 1949 2,481,208

Eberle Sept. 6, 1949 

1. A METHOD FOR CATALYTICALLY TREATING A SATURATED HYDROCARBON MATERIAL CONTAINING SATURATED FLUORINE CONTAINING ORGANIC COMPOUNDS AS IMPURITY FOR THE REMOVAL OF SAID IMPURITY COMPRISING MAINTAINING A BODY OF AT LEAST ONE FINELY DIVIDED METAL CATALYST SELECTED FROM THE GROUP OF METALS CONSISTING OF ZINC, MAGNESIUM, IN A FLUIDMIUM, COPPER, LEAD AND ALUMINUM, IN A FLUIDIZED CONDITION IN A TREATING ZONE AT A TEMPERATURE BETWEEN THE LIMITS OF 150* F. AND 350* F., PASSING SAID SATURATED HYDROCARBON MATERIAL CONTAINING SAID IMPURITY IN A VAPOROUS CONDITION AT A TEMPERATURE BETWEEN THE LIMITS OF 150* F. AND 350* F. INTO SAID BODY OF FLUIDIZED METAL CATALYST IN SAID ZONE TO DECOMPOSE THE ORGANIC FLUORINE COMPOUNDS AND LIBERATE HYDROGEN FLUORIDE, IMMEDIATELY SEPARATING THE LIBERATED HYDROGEN FLUORIDE FROM THE HYDROCARBON VAPORS BY PASSING THE EFFLUENT VAPORS FROM THE FLUIDIZED METAL CATALYST THROUGH A FLUIDIZED BODY OF ACTIVATED CARBON IN SAID ZONE ABOVE AND IN CONTACT WITH SAID METAL CATALYST, AND REMOVING TREATED HYDROCARBON MATERIAL FROM THE BODY OF ACTIVATED CARBON IN SAID ZONE AS THE PRODUCT OF THE PROCESS. 